J. Braz. Chem. Soc., Vol. 9, No. 1, 199-210, 1998. © 1998 Soc. Bras.

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Review

Transesterification of Vegetable Oils: a Review

Ulf Schuchardta, Ricardo Serchelia, and Rogério Matheus Vargas*b

a
Instituto de Química, Universidade Estadual de Campinas, C.P. 6154,
13083-970 Campinas - SP, Brazil
b
Instituto de Química, Universidade Federal da Bahia, Campus de Ondina,
40170-290 Salvador - BA, Brazil

Received: May 9, 1997

A transesterificação de óleos vegetais com metanol, bem como as principais aplicações de ésteres
metílicos de ácidos graxos, são revisadas. São descritos os aspectos gerais desse processo e a
aplicabilidade de diferentes tipos de catalisadores (ácidos, hidróxidos, alcóxidos e carbonatos de
metais alcalinos, enzimas e bases não-iônicas, como aminas, amidinas, guanidinas e
triamino(imino)fosforanos). Enfoque especial é dado às guanidinas, que podem ser facilmente
heterogeneizadas em polímeros orgânicos. No entanto, as bases ancoradas lixiviam dos polímeros.
Novas estratégias para a obtenção de guanidinas heterogeneizadas mais resistentes à lixiviação são
propostas. Finalmente, são descritas várias aplicações para ésteres de ácidos graxos, obtidos por
transesterificação de óleos vegetais.

The transesterification of vegetable oils with methanol as well as the main uses of the fatty acid
methyl esters are reviewed. The general aspects of this process and the applicability of different
types of catalysts (acids, alkaline metal hydroxides, alkoxides and carbonates, enzymes and
non-ionic bases, such as amines, amidines, guanidines and triamino(imino)phosphoranes) are
described. Special attention is given to guanidines, which can be easily heterogenized on organic
polymers. However, the anchored catalysts show leaching problems. New strategies to obtain
non-leaching guanidine-containing catalysts are proposed. Finally, several applications of fatty acid
esters, obtained by transesterification of vegetable oils, are described.

Keywords: transesterification, fatty acid methyl esters, non-ionic bases, heterogenization

General Aspects of Transesterification base) accelerates considerably the adjustment of the equi-
librium. In order to achieve a high yield of the ester, the
Transesterification is the general term used to describe
alcohol has to be used in excess.
the important class of organic reactions where an ester is
The applicability of transesterification is not restricted
transformed into another through interchange of the alkoxy
to laboratory scale. Several relevant industrial processes
moiety. When the original ester is reacted with an alcohol,
use this reaction to produce different types of compounds1.
the transesterification process is called alcoholysis
An example is the production of PET (polyethylene tere-
(Scheme 1)1. In this review, the term transesterification will
phthalate), which involves a step where dimethylterephtha-
be used as synonymous for alcoholysis of carboxylic esters,
late is transesterified with ethylene glycol in the presence
in agreement with most publications in this field. The
of zinc acetate as catalyst (Scheme 2)2. Furthermore, a large
transesterification is an equilibrium reaction and the trans-
number of acrylic acid derivatives is produced by tran-
formation occurs essentially by mixing the reactants. How-
sesterification of methyl acrylate with different alcohols, in
ever, the presence of a catalyst (typically a strong acid or
the presence of acid catalysts3-6.
catalyst If the alcohol and the ester groups are present in the
RCOOR' + R"OH RCOOR" + R'OH same molecule simple lactones7,8 or macrocycles9-10 are
Scheme 1. General equation for a transesterification reaction. formed by an intramolecular transesterification, as shown
200 Schuchard et al. J. Braz. Chem. Soc.

O O HO - 2 CH3OH O O
+ 2 HO OH
O O OH O O
Scheme 2. Transesterification of dimethylterephthalate with ethylene glycol.

in Scheme 3. Further transesterification reactions can be

found in the literature, in which metal alkoxides11-16, alu- p-toluene
minum isopropoxide17-19, tetraalkoxytitanium com- H sulfonic acid
H H
pounds20-22 and organotin alkoxides23,24 are applied as
OH
catalysts. O

Transesterification of Vegetable Oils OH

HO O
In the transesterification of vegetable oils, a triglyceride O O
reacts with an alcohol in the presence of a strong acid or
base, producing a mixture of fatty acids alkyl esters and p-toluene
glycerol25,26 (Scheme 4). The overall process is a sequence sulfonic acid
OH O O
of three consecutive and reversible reactions, in which di-
and monoglycerides are formed as intermediates26. The OR
stoichiometric reaction requires 1 mol of a triglyceride and
3 mol of the alcohol. However, an excess of the alcohol is O
used to increase the yields of the alkyl esters and to allow
Scheme 3. Examples of intramolecular transesterification reactions,
its phase separation from the glycerol formed. forming lactones or macrocycles.
Several aspects, including the type of catalyst (alkaline
or acid), alcohol/vegetable oil molar ratio, temperature, other hand, an excessive amount of alcohol makes the
purity of the reactants (mainly water content) and free fatty recovery of the glycerol difficult, so that the ideal alco-
acid content have an influence on the course of the tran- hol/oil ratio has to be established empirically, considering
sesterification and will be discussed below, based on the each individual process.
type of catalyst used. The mechanism of the acid-catalyzed transesterifica-
tion of vegetable oils is shown in Scheme 5, for a mono-
Acid-Catalyzed Processes glyceride. However, it can be extended to di- and
The transesterification process is catalyzed by BrØn- triglycerides31. The protonation of the carbonyl group of
sted acids, preferably by sulfonic27 and sulfuric ac- the ester leads to the carbocation II which, after a nucleo-
ids26,28,29. These catalysts give very high yields in alkyl philic attack of the alcohol, produces the tetrahedral inter-
esters, but the reactions are slow, requiring, tipically, tem- mediate III, which eliminates glycerol to form the new ester
peratures above 100 °C and more than 3 h to reach complete IV, and to regenerate the catalyst H+.
conversion30. Pryde et al.26 showed that the methanolysis According to this mechanism, carboxylic acids can be
of soybean oil, in the presence of 1 mol% of H2SO4, with formed by reaction of the carbocation II with water present
an alcohol/oil molar ratio of 30:1 at 65 °C, takes 50 h to in the reaction mixture. This suggests that an acid-catalyzed
reach complete conversion of the vegetable oil (> 99%), transesterification should be carried out in the absence of
while the butanolysis (at 117 °C) and ethanolysis (at 78 °C), water, in order to avoid the competitive formation of car-
using the same quantities of catalyst and alcohol, take 3 and boxylic acids which reduce the yields of alkyl esters.
18 h, respectively.
The alcohol/vegetable oil molar ratio is one of the main Base-Catalyzed Processes
factors that influences the transesterification. An excess of The base-catalyzed transesterification of vegetable oils
the alcohol favors the formation of the products. On the proceeds faster than the acid-catalyzed reaction26,30. Due
ROCOR'
H2C OCOR' catalyst + H2C OH
HC OCOR" + 3 ROH ROCOR" + HC OH
+
H2C OCOR"' H2C OH
ROCOR"'
triglyceride alcohol mixture of alkyl glycerol
esters
Scheme 4. Transesterification of vegetable oils.
Vol. 9, No. 1, 1998 Transesterification of Vegetable Oils 201

+
O +
OH OH
H
+
R' OR'' R' OR'' R' OR''
I II

OH OH + O
R + H - H / R''OH
+ O R' O
R' +
OR'' H R' OR
OR'' R
O III IV
R''
' = OH ; glyceride
OH
R' = carbon chain of the fatty acid
R = alkyl group of the alcohol
Scheme 5. Mechanism of the acid-catalyzed transesterification of vegetable oils.

-
ROH + B RO + BH+ (1)

R'COO CH2 R'COO CH2

-
R"COO CH + OR R"COO CH OR (2)
H2 C OCR"' H2C O C R"'
O -
O

R'COO CH2 R'COO CH2

R"COO CH OR + ROOCR"' (3)
R"COO CH
H2C O C R"' H2C O
-
-
O

R'COO CH2 R'COO CH2

+ BH
+
R"COO CH + B (4)
R"COO CH
- H2 C OH
H2 C O

Scheme 6. Mechanism of the base-catalyzed transesterification of vegetable oils.

to this reason, together with the fact that the alkaline
catalysts are less corrosives than acidic compounds, indus-
trial processes usually favor base catalysts, such as alkaline
metal alkoxides26,30,32 and hydroxides29,33-36 as well as so-
dium or potassium carbonates37-39.
The mechanism of the base-catalyzed transesterifica-
tion of vegetable oils is shown in Scheme 6. The first step
(Eq. 1) is the reaction of the base with the alcohol, produc-
ing an alkoxide and the protonated catalyst. The nucleo-
philic attack of the alkoxide at the carbonyl group of the
triglyceride generates a tetrahedral intermediate (Eq.
2)11,40, from which the alkyl ester and the corresponding
anion of the diglyceride are formed (Eq. 3). The latter
deprotonates the catalyst, thus regenerating the active spe-
cies (Eq. 4), which is now able to react with a second
molecule of the alcohol, starting another catalytic cycle.
Diglycerides and monoglycerides are converted by the
same mechanism to a mixture of alkyl esters and glycerol.
Alkaline metal alkoxides (as CH3ONa for the
methanolysis) are the most active catalysts, since they give
very high yields (> 98%) in short reaction times (30 min)
even if they are applied at low molar concentrations (0.5
mol%). However, they require the absence of water which
makes them inappropriate for typical industrial proc-
esses30. Alkaline metal hydroxides (KOH and NaOH) are
cheaper than metal alkoxides, but less active. Nevertheless,
they are a good alternative since they can give the same
high conversions of vegetable oils just by increasing the
catalyst concentration to 1 or 2 mol%. However, even if a
water-free alcohol/oil mixture is used, some water is pro-
202 Schuchard et al. J. Braz. Chem. Soc.

duced in the system by the reaction of the hydroxide with
the alcohol. The presence of water gives rise to hydrolysis
of some of the produced ester, with consequent soap for-
mation (Scheme 7). This undesirable saponification reac-
tion reduces the ester yields and considerably difficults the
recovery of the glycerol due to the formation of emul-
sions30.
Potassium carbonate, used in a concentration of 2 or 3
mol% gives high yields of fatty acid alkyl esters and
reduces the soap formation38. This can be explained by the
formation of bicarbonate instead of water (Scheme 8),
which does not hydrolyse the esters.
Lipase-Catalyzed Processes
Due to their ready availability and the ease with which
they can be handled, hydrolytic enzymes have been widely
applied in organic synthesis. They do not require any
coenzymes, are reasonably stable, and often tolerate or-
ganic solvents. Their potential for regioselective and espe-
cially for enantioselective synthesis makes them valuable
tools41.
Although the enzyme-catalyzed transesterification
processes are not yet commercially developed, new results
have been reported in recent articles and patents42-48. The
common aspects of these studies consist in optimizing the
reaction conditions (solvent, temperature, pH, type of mi-
croorganism which generates the enzyme, etc) in order to
establish suitable characteristics for an industrial applica-
tion. However, the reaction yields as well as the reaction
times are still unfavorable compared to the base-catalyzed
reaction systems.
Non-Ionic Base-Catalyzed Processes
In order to obtain milder reaction conditions and to
simplify manipulations, a great number of organic bases
has been developed and used as catalyst or reactant for
organic syntheses. Among these bases, amines such as
triethylamine49,50, piperidine49, 1,2,2,6,6-pentamethylpi-
O O
+ H2O
R' OR R' OH
O O
+ NaOH
R' OH R' ONa
R' = carbon chain of the fatty acid
R = alkyl group of the alcohol
peridine49,51, pyridine49,50,51, 2,6-di-tert-butylpyridine49,51
and 4-dimethyl-aminopyridine1,52 (DMAP); amidines such
as 1,8-diazabicyclo[5.4.0]undec-7-ene1,49,50,51 (DBU) and
1,5-diazabicyclo[4.3.0]non-5-ene49,51,53 (DBN); guanidi-
nes such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene50,54 (TBD),
1,1,3,3-tetramethylguanidine55,56,57 (TMG), 1,1,2,3,3-pen-
tabutylguanidine58 (PBG), 1,3-diphenylguanidine59, 1,2,3-
triphenylguanidine60,61 and amino- and nitroguanidines62;
triamino(imino)phosphoranes such as tert-butylimino-2-
diethylamino-1,3-dimethyl-perhydro-1,3,2- diazaphos-
phorane51 (BEMP) and tris(dimethylamino)methylimino-
phosphorane51 (Me7P), shown in Scheme 9, are frequently
used in organic synthesis.
The activity and efficiency of such non-ionic bases as
catalysts for the transesterification of vegetable oils were
studied. In a first series of studies, the catalytic activity of
some guanidines was compared to that observed using
other bases such as the amidines DBU and DBN, and the
triamino(imino)phosphoranes BEMP and Me7P63. It was
observed that TBD, even if applied at only 1 mol%, pro-
duces more than 90% of methyl esters after 1 h. Using the
other bases, under the same experimental conditions, the
yields were not higher than 66% (Table 1). The order of the
catalytic activity is not directly related to the relative
basicity of these compounds, since BEMP and Me7P should
be the more efficient catalysts, followed by TBD. However,
the guanidines are more active catalysts and the activity
follows their relative basicity.
According to the observed results and to the mechanism
of the base-catalyzed transesterification (Scheme 6), it
seems that the good performance of TBD, when compared
to BEMP and Me7P, is related to its kinetic activity. The
catalytic site (unshared electron pair of the sp2 N) of TBD
is practically unhindered (Scheme 10), allowing an easy
access of the methanol for proton transfer, while the steric
Table 1. Comparison of the catalytic activity of some guanidines, ami-
dines and triamino(imimo)phosphoranes in the transesterification of rape-
seed oil with methanol.
+ ROH Catalyst Relative pKa Yield (%)
basicity51 (CH3CN)49 after 1 h a
TBD 150 25.9 91
+ H2O
BEMP 6873 not available 66
Me7P 4762 27.52 63
MTBD 43.65 25.43 47

Scheme 7. Saponification reaction of the produced fatty acid alkyl esters.

DBU 3.4 24.32 32
TMG 0.95 23.30 18
K2CO3 + ROH ROK + KHCO3
DBN 1 23.79 4.5
R = alkyl group of the alcohol
a: conditions: 8.00 g (27.2 mmol) of rapeseed oil, 2.00 g (62.5 mmol) of
Scheme 8. Reaction of potassium carbonate with the alcohol. methanol, 1 mol% of catalyst, 70 °C.
Vol. 9, No. 1, 1998 Transesterification of Vegetable Oils 203

N N N N N
P
N N N N
N N
H

TBD DBU DBN BEMP

N N N H H
P N N N N
N N H H
N N H17C8
CH3 N N

Me7P MTBD DCOG TCG

Scheme 9. Molecular structures of some non-ionic organic bases.

H H
H
H
H :
N H H N
: H
H H N H
: P N
N N H P N
N N N
H N
H
TBD BEMP Me7P

Scheme 10. Steric hindrance of TBD, BEMP and Me7P.

hindrance shown by the triamino(imino)phosphoranes is so Table 2. Comparison between TBD and the conventional inorganic
significant that they are practically inert to alkylating catalysts.
agents, such as isopropyl bromide, as well as extremely
resistant to react with thionyl chloride and thiophosgene51.
Catalyst Yield (%) after 1 ha
Other bases such as DMAP, pyridine and triethylamine NaOH (1 mol%) 98.7
were also tested. However, even at 5 mol%, these amines K2CO3 (1 mol%) 84.0
did not give satisfactory yields. DMAP was the most active
within this series, producing only 20% of methyl esters K2CO3 (2 mol%) 90.3
after 1 h. K2CO3 (3 mol%) 92.4
In a second series of studies, the catalytic activity of TBD (1 mol%) 89.0
TBD was compared to that observed for typical industrial
catalysts (e.g. NaOH and K2CO3)37-39. The results of this TBD (2 mol%) 91.4
study63 are shown in Table 2. The reaction yields obtained TBD (3 mol%) 93.0
with TBD were close to those observed with NaOH and no
undesirable by-products such as soaps (easily formed when a: 8.00 g (27.2 mmol) of rapeseed oil, 2.00 g (62.5 mmol) of methanol,
1 h, 70 °C.
alkaline metal hydroxides are used) were observed. When
compared to potassium carbonate, TBD was always more Due to the excellent performance of TBD in the tran-
active, even at low molar concentrations. Although TBD is sesterification of vegetable oils, the catalytic activity of
less active than sodium methoxide (at only 0.5%, CH3ONa other alkylguanidines was also investigated, in order to
produces more than 98% of methyl esters after 30 min), its establish and understand all factors that may affect their
use does not require any special condition. catalytic properties. In a third series of studies, the catalytic
204 Schuchard et al. J. Braz. Chem. Soc.

activity of several alkylguanidines was compared64. biguanidine (PCBG) is even more active than TCG, as a
TBD was always the most active, however, 1,3-dicy- 82% yield of methyl esters is obtained with PCBG after 1 h,
clohexyl-2-n-octylguanidine (DCOG), 1,1,2,3,3- compared to 69% with TCG under the same conditions66.
pentamethylguanidine (PMG), 7-methyl-1,5,7-triaz-
abicyclo[4.4.0]dec-5-ene (MTBD) and 1,2,3-tricyclo- Heterogeneously Catalyzed Processes
hexylguanidine (TCG), also showed a good catalytic The advantage of using guanidines in the transesterifi-
performance64. The activity order of the catalysts cation of vegetable oils is the possibility to heterogenize
TBD > TCG > DCOG > MTBD > PMG (Table 3) them on organic polymers. Schuchardt et al. tested princi-
corresponds to their relative base strength, which is
pally cellulose and poly(styrene/divinylbenzene), but also
increased by structural factors such as number and
polyuretanes and other organic polymers allow the suitable
type of substituents (cyclic or acyclic chain) 51. The
incorporation of guanidines. The heterogenization of
excellent performance of DCOG and TCG is also as-
guanidines on organic polymers and their use in the tran-
signed to the high symmetry of their guanidinium
cations, as observed earlier for the symmetric 1,2,3- sesterification of vegetable oils were described in a pat-
trimethylguanidine 65. ent67.
Results obtained in the transesterification of soybean The heterogenization of unsubstituted guanidines can
oil with methanol show that 1,2,3,4,5-pentacyclohexyl- be achieved by their reaction with microcrystalline cellu-
lose activated by cyanuric chloride at the C-6 position
Table 3. Transesterification of rapeseed oil with methanol using the most (Scheme 11). After deprotonation of the guanidinium salt
active alkylguanidines as catalysts. formed, the guanidine-containing cellulose shows a
slightly reduced activity, compared to guanidine in homo-
Yields (%) after 1 ha
geneous phase, giving a conversion of 30% after 1 h, when
Catalyst 1 mol% 2 mol% 3 mol% used at 5 mol%68. This guanidine-containing cellulose was
TBD 90 91 93 used in a continuous reactor containing 100 g of the cata-
lyst. An alcohol/oil mixture of 2:1 was pumped at 60 °C
DCOG 74 80 92 with a rate of 0.48 L/h. In the first hour the methyl esters
TCG 64 91 92 were obtained with high yields and the phase separation
MTBD was quick69. After this, however, the reaction was incom-
47 74 -
plete and the phase separation difficult. This could be due
PMG 49 67 90 either to leaching of the catalyst or to its irreversible
a: conditions: 8.00 g (27.2 mmol) of rapeseed oil, 2.00 g (62.5 mmol) of protonation. As no leaching tests were performed, no defi-
methanol, 1 mol% of catalyst, 70 °C. nite reason can be given at this point.

H Cl
CH2OH
O H
O N N
HO +
H O
H OH Cl N Cl
H

- HCl

Cl Cl

N N N N
H H
H H
N Cl N
N N Cl-
CH2O CH2O C NH2
O H H2N NH2 O H +
HO O O NH2
HO
H O H O
H OH H OH
H H

Scheme 11. Heterogenization of guanidine on activated microcrystalline cellulose.

Vol. 9, No. 1, 1998 Transesterification of Vegetable Oils 205

The catalytic performance of some alkylguanidines het- polymer II and polymer III was even less active than
erogenized on different substituted polystyrenes was inves- polymer I70.
tigated70. The guanidine-containing polymers (Scheme 12) Despite less active than their homogeneous analogues,
were used in the transesterification of soybean oil with all polymer-containing guanidines could be reused in sev-
methanol in several consecutive catalytic cycles. The eral consecutive reaction cycles70. However, a loss of ac-
guanidines heterogenized on gel-type poly(sty- tivity was observed, mainly due to leaching of the anchored
rene/divinylbenzene) with 1 meq Cl/g (polymers I and II)
base from the polymers, as mentioned above. Polymers I
showed a slightly lower activity than their homogeneous
and II have the guanidine moiety bound to the benzylic CH2
analogues but allowed the same high conversions after
group of the polystyrene. After the protonation of the base,
prolonged reaction times. However, they slowly leached
from the polymers, allowing only nine catalytic cycles. The the electrophilic character of the methylene group is in-
guanidines heterogenized on linear polystyrene with the
Table 4. Total turnover numbers and turnover frequencies (after 1 h)
use of a ‘spacer-arm’ (polymers III, IV), were less active.
observed with guanidine-containing polymers in the transesterification of
Polymer V, which is symmetrically substituted showed an soybean oil with methanol.
activity as high as polymer I. When another methyl group
was introduced (polymer VI) its activity was slightly re- Catalyst total turnover turnover frequency
duced. Furthermore, all polymers with a ‘spacer-arm’ suf- numbera,b (h-1)c
fered substitution reactions during the recycling (number of cycles)
experiments to form inactive hexasubstituted guanidinium I 124 (9) 15
compounds. A summary of the catalytic performance of
these polymers is shown in Table 4. II 118 (9) 12
The lower activity of the guanidine-containing poly- III 36 (5) 13
mers I and II, when compared to their homogeneous ana-
logues, is probably due to the hydrophobicity of the IV 30 (4) 12
polymer chain which reduces the concentration of the V 84 (6) 15
methanol at the active sites. However, at prolonged reaction
VI 42 (7) 14
times, the efficiency of the anchored catalysts is practically
the same. The use of a ‘spacer-arm’ (polymers III-VI) was a: turnover number: mol of products/ mol of catalyst.
expected to improve the performance of the heterogenized b: conditions: 1 eq. of soybean oil, 6.9 eq. of methanol, 5 mol% of base,
catalyst. However, polymer IV showed the same activity as 70 °C. c: turnover frequency: turnover number/ reaction time.

N(CH3)2
P CH2 N P (CH2)5CH2 N
N N(CH3)2
N IV

I
N(CH3)2 N
P CH2 N P (CH2)5CH2 N
N(CH3)2 H N H
II V

N
P (CH2)5CH2 N P (CH2)5CH2 N
N CH3 N H
N

III VI

P = polymer chain

Scheme 12. Molecular structures of some guanidine-containing polystyrenes.

206
creased, thus becoming more susceptible to nucleophilic
attack by methoxide ions present in the reaction medium.
This attack results in the removal of the guanidine moiety
from the polymer as shown in Scheme 13. The leaching of
the guanidines from the other polymers follows a similar
mechanism.
For the polymers containing a ‘spacer-arm’, there is
an additional factor that accelerates the deactivation of
the supported catalysts. The anchored bases can react
with electrophilic functional groups which are further
away on the polymer chain, producing inactive hexasub-
stituted guanidinium compounds64, as shown in Scheme
14. However, it is possible to deprotonate these hexasub-
stituted guanidinium compounds, which should give
doubly anchored active guanidines whose leaching is
less probable.
In order to circumvent the leaching of the guanidines
from the polymers, Schuchardt et al. encapsulate TCG by
the reaction of dicyclohexylcarbodiimide and cyclohexy-
lamine in the supercages of a hydrophobic Y zeolite. The
encapsulated guanidine showed a good catalytic activity in
the addition reaction of benzaldehyde to acetone71. How-
ever, its activity in the transesterification of vegetable oils
is low (14% conversion after 5 h72), as the diffusion of the
triglycerides through the channels of the Y zeolite is slow
due to steric hindrance.
CH3O-
H
CH2 N
+
N(CH3)2
Scheme 13. Leaching of the guanidine moiety from the polymers.
Br
N N
R R
N N
R H
Scheme 14. Reaction of the heterogenized guanidines III-VI with unreacted 6-bromohexyl substituents.
Schuchard et al. J. Braz. Chem. Soc.
Fatty Acid Alkyl Esters as Feedstocks for In-
dustry
Fatty acid methyl esters can be transformed into a lot of
useful chemicals, and raw materials for further synthesis73,
as shown in Scheme 15. The alkanolamides, whose produc-
tion consumes the major part of the methyl esters produced
in the world, have a direct application as non-ionic surfac-
tants, emulsifying, thickening and plastifying agents, etc73.
The fatty alcohols are applied as pharmaceutical and cos-
metics additives (C16-C18)73, as well as lubricants and
plastifying agents (C6-C12), depending on the length of
their carbon chain. The isopropyl esters are also applied as
plastifying agents and emollients. However, they can not
be produced in a convenient way by esterification of fatty
acids, as an azeotrope formed by water and isopropanol
avoids the recycling of the alcohol. The fatty acid methyl
esters are further used in the manufacture of carbohydrate
fatty acid esters (sucrose polyesters), which can be applied
as non-ionic surfactants or edible non-calorific oils74-77,
and can be used as an alternative fuel substitute for diesel
engines (biodiesel)28-30, 78-80. These two applications will
be discussed separately.
The glycerol also has important applications, in cosmet-
ics, toothpastes, pharmaceuticals, food, lacquers, plastics,
CH2 OCH3
N(CH3)2
+
NH
H3C CH3
N N
H3C CH3
Br-
N N
R R
R H
Vol. 9, No. 1, 1998 Transesterification of Vegetable Oils 207

alkanolamides isopropylic esters

RC(O)N(CH2CH2OH)2 RCO(O)CH(CH3)2

HN(CH2CH2OH)2 HOCH(CH3)2

RCOOCH3
fatty acid
methyl
esters

H2 /CuCr2O4 sucrose

RCH2OH sucrose polyesters

fatty alcohols
OR
RO O
RO
OR
O
biodiesel OR
RO O

OR
OR

R = carbon chain
of the fatty acid
Scheme 15. Some fatty acid methyl esters applications.

alkyl resins, tobacco, explosives, cellulose processing,
etc81.
Fatty Acid Alkyl Esters as Biodiesel
With exception of hydroelectricity and nuclear energy,
the major part of all energy consumed worldwide comes
from petroleum, charcoal and natural gas. However, these
sources are limited, and will be exhausted by the end of the
next century33. Thus, looking for alternative sources of
energy is of vital importance.
Vegetable oils are a renewable and potentially inex-
haustible source of energy with an energetic content close
to diesel fuel82. Historically, it is believed that Rudolf
Diesel himself82 started research with respect to the use of
vegetable oils as fuel for diesel engines. In the following
decades, the studies became more systematic and, nowa-
days, much is known about its use as fuel. Despite energeti-
cally favorable, the direct use of vegetable oils in fuel
engines is problematic. Due to their high viscosity (about
11 to 17 times higher than diesel fuel) and low volatility,
they do not burn completely and form deposits in the fuel
injector of diesel engines. Furthermore, acrolein (a highly
toxic substance) is formed through thermal decomposition
of glycerol32, 83-87. Different ways have been considered to
reduce the high viscosity of vegetable oils:
• dilution of 25 parts of vegetable oil with 75 parts of
diesel fuel32;
• microemulsions with short chain alcohols (e.g. etha-
nol or methanol)32;
• thermal decomposition, which produces alkanes,
alkenes, carboxylic acids and aromatic com-
pounds87;
• catalytic cracking, which produces alkanes, cycloal-
kanes and alkylbenzenes84, and
• transesterification with ethanol or methanol88,89.
Among all these alternatives, the transesterification
seems to be the best choice, as the physical characteristics
of fatty acid esters (biodiesel) are very close to those of
diesel fuel32 and the process is relatively simple. Further-
more, the methyl or ethyl esters of fatty acids can be burned
directly in unmodified diesel engines, with very low de-
posit formation37,38,79,80,82.
Several types of vegetable oils, with a diversified com-
position in fatty acids, can be used for the preparation of
biodiesel. Soybean26,30,32,84, rapeseed38,78,79, sunflower28
and palm29,37 oils are the most studied. However, there are
no technical restrictions to the use of other types of vege-
table oils. Considering the type of the alcohol, the use of
methanol is advantageous as it allows the simultaneous
separation of glycerol. The same reaction using ethanol is
208 Schuchard et al.
more complicated as it requires a water-free alcohol, as
well as an oil with a low water content, in order to obtain
glycerol separation.
Normally, methanol is used as it is the cheapest alcohol
in most countries. However, in Brazil it is advantageous to
use anhydrous ethanol90, which is already produced in large
quantities to be mixed with gasoline. The guanidines de-
scribed here have been shown to be efficient catalysts for
the transesterification of vegetable oils with commercial
anhydrous ethanol69.
Fatty Acid Esters of Carbohydrates
The fatty acid esters of carbohydrates can be obtained
by esterification of fatty acids, or by transesterification of
their correspondent alkyl esters with carbohydrates (or
other polyols) and constitute an important class of synthetic
organic products. Their physico-chemical properties,
which depend on the number and type of the esterified fatty
acid, allow their application as non-ionic biodegradable
surfactants74, or as substitutes of vegetable oils for non-
calorific diets75-77. The mixture of hexa-, hepta- and oc-
taesters of sucrose, known as ‘‘olestra’’, has been studied
for more than 20 years75. Their physical properties are very
close to those of the triglycerides with similar esterified
fatty acids, and the resistance to the pancreatic lipase
(which avoids the absorption by the digestive tract) allows
its application as non-calorific edible oil75.
Typically, the sugar polyesters (SPE) are prepared
through base-catalyzed transesterification of carbohy-
drates with fatty acid methyl esters, using sodium methox-
ide as catalyst91-95. However, some of these methods
require very high temperatures (above 100 °C) and toxic
low-volatile solvents (e.g. DMF and DMSO), compromis-
ing the final product for human consumption. Alterna-
tively, Rizzi and Taylor91, based on the studies of Feuge et
al.96, developed a two-stage solvent-free process, in which
the SPE are synthesized by transesterification, using so-
dium hydride, Na-K alloy and soaps as catalyst. Despite the
very good reaction yields (about 90%), this process still
shows some inconveniences such as the need for high
temperatures (150 °C), and the difficulty to purify the final
product (the soaps are not easily eliminated).
Another solvent-free process was proposed by Akoh
and Swanson93, in which sorbitol and trealose octaoleate
are produced in excellent yields (> 90%) through inter-
esterification reactions of the correspondent acetates and
methyl oleate, using Na as catalyst. The temperature
(110 °C) and reaction time (2.5 h) are lower when com-
pared to the previous work. However, the catalyst requires
a water-free system in order to avoid its deactivation.
New milder solvent-free catalytic systems are being
developed, and consist in the use of guanidine as catalyst,
which furnished good preliminary results97.
J. Braz. Chem. Soc.
Conclusions and Perspectives
The industrial homogeneous catalysts will have to be
substituted in the near future by heterogeneous catalysts
due to environmental reasons. Good strong-base heteroge-
neous catalysts are still in development. One possibility
would be the use of zeolites with strong basic sites98. Here
the use of guanidines anchored on organic polymers was
emphasized. To avoid leaching of the guanidine, however,
it should be doubly anchored to the polymers. Another
possibility would be the encapsulation of guanidines in an
appropriate inorganic matrix. The Y zeolite is not appro-
priate for this purpose as the rather small diameter of its
pore system slows down the diffusion of the fatty acid
triglycerides.
Acknowledgments
The authors acknowledge financial support from
FAPESP and fellowships from FAPESP and CNPq. Part of
our work has been developed with financial support from
the Commission of the European Communities.
References
1. Otera, J. Chem. Rev. 1993, 93, 1449.
2. Weissermel, K.; Arpe, H.-J. In Industrial Organic
Chemistry, VCH Verlagsgesellschaft, 2nd Ed., Wein-
hein, 1993, p 396.
3. Rehberg, C.E.; Fisher, C.H. J. Am. Chem. Soc. 1944,
66, 1203.
4. Rehberg, C.E.; Faucette, W.A.; Fisher, C.H. J. Am.
Chem. Soc. 1944, 66, 1723.
5. Rehberg, C.E. Org. Synth. 1955, III, 146.
6. Haken, J.K. J. Appl. Chem. 1963, 13, 168.
7. Shishido, K.; Irie, O.; Shibuya, M. Tetrahedron Lett.
1992, 33, 4589.
8. Chavan, S.P.; Zubaidha, P.K.; Ayyangar, N.R. Tetra-
hedron Lett. 1992, 33, 4605.
9. Vatlas, I.; Harrison, I.T.; Tökés, L.; Fried, J.H.; Cross,
A.D. J. Org. Chem. 1968, 33, 4176.
10. Narasaka, K.; Yamaguchi, M.; Mukaiyama, T. Chem.
Lett. 1977, 959.
11. Taft, R.W. Jr.; Newman, M.S.; Verhoek, F.H. J. Am.
Chem. Soc. 1950, 72, 4511.
12. Billman, J.H.; Smith, W.T. Jr.; Rendall, J.L. J. Am.
Chem. Soc. 1947, 69, 2058.
13. Haken, J.K. J. Appl. Chem. 1966, 16, 89.
14. Frank, R.L.; Davis, H.R. Jr.; Drake, S.S.; McPherson,
J.B. Jr. J. Am. Chem. Soc. 1944, 66, 1509.
15. Wulfman, D.S.; McGiboney, B.; Peace, B.W. Synthe-
sis 1972, 49.
16. Rossi, R.A.; de Rossi, R.H. J. Org. Chem. 1974, 39,
855.
17. Rehberg, C.E.; Fisher, C.H. J. Org. Chem. 1947, 12,
226.
Vol. 9, No. 1, 1998 Transesterification of Vegetable Oils
18. Said, A. Chimia 1974, 28, 234.
19. Brenner, M.; Huber, W. Helv. Chem. Acta. 1953, 36,
1109.
20. Seebach, D.; Hungerbühler, E.; Naef, R.; Schnurren-
berger, P.; Weidmann, B.; Züger, M. Synthesis 1982,
138.
21. Imwinkelried, R.; Schiess, M.; Seebach, D. Org.
Synth. 1987, 65, 230.
22. Blandy, C.; Gervais, D.; Pellegatta, J.-L.; Gillot, B.;
Guiraud, R. J. Mol. Catal. 1991, 64, L1-L6.
23. Pereyre, M.; Colin, G.; Delvigne, J.-P. Bull. Soc.
Chim. Fr. 1969, 262.
24. Otera, J.; Yano, T.; Atsuya, K.; Nosaki, H. Tetrahe-
dron Lett. 1986, 27, 2383.
25. Wright, H.J.; Segur, J.B.; Clark, H.V.; Coburn, S.K.;
Langdon, E.E.; DuPuis, E.N. Oil & Soap 1944, 145.
26. Freedman, B.; Butterfield, R.O.; Pryde, E.H. J. Am.
Oil Chem. Soc. 1986, 63, 1375.
27. Stern, R.; Hillion, G.; Eur. Pat. Appl. EP 356,317 (Cl.
C07C67/56), 1990; Chem. Abstr. 113: P58504k
(1990).
28. Harrington, K.J.; D’Arcy-Evans, C. Ind. Eng. Chem.
Prod. Res. Dev. 1985, 24, 314.
29. Graille, J.; Lozano, P.; Pioch, D.; Geneste, P. Oléagi-
neux 1986, 41, 457.
30. Freedman, B.; Pryde, E.H.; Mounts, T.L. J. Am. Oil
Chem. Soc. 1984, 61, 1638.
31. Stoffel, W.; Chu, F.; Ahrens, E.H. Jr. Anal. Chem.
1959, 31, 307.
32. Schwab, A.W.; Baghy, M.O.; Freedman, B. Fuel
1987, 66, 1372.
33. Aksoy, H.A.; Becerik, I.; Karaosmanoglu, F.; Yamaz,
H.C.; Civelekoglu, H. Fuel 1990, 69, 600.
34. Tanaka, Y.; Okabe, A.; Ando, S. US. Pat. Appl.
4,303,590 (Cl. C11C3/02), 1981; Chem. Abstr. 94: P
139250r (1981).
35. Gaskoks-Vertrieb GmbH; Austrian AT 387,399
(Cl.C11C3/04), 1989; Chem. Abstr. 110: P196201y
(1989).
36. Wimmer, T. PCT. Ind. Appl. WO 9309,212 (Cl
C11C3/04), 1993; Chem. Abstr. 120: P10719b (1994).
37. Graille, J.; Lozano, P.; Pioch, D.; Geneste, P. Oléagi-
neux 1985, 40, 271.
38. Filip, V.; Zajic, V.; Smidrkal, J. Rev. Fr. Corps Gras
1992, 39, 91.
39. Bajwa, U.; Bains, G.S. J. Food. Sci. Technol. 1987,
24, 81.
40. Guthrie, J.P. J. Am. Chem. Soc. 1991, 113, 3941.
41. Drauz, K.; Waldmann, H.; Sauerbrei, B. In Applied
Homogeneous Catalysis with Organometallic Com-
pounds; Cornils, B.; Herrmann, W.A., ed.; vol. 2,
VCH Verlagsgessellschaft, Weinheim, 1996, p 769.
42. Posorske, L.H. J. Am. Oil Chem. Soc. 1984, 61, 1758.
209
43. Posorske, L.H.; Le Febvre, G.K.; Miller, C.A.; Han-
sen, T.T.; Glenvig, B.L. J. Am. Oil Chem. Soc. 1988,
65, 922.
44. McNeill, G.P.; Shimizu, S.; Yamane, T. J. Am. Oil
Chem. Soc. 1991, 68, 1.
45. McNeill, G.P.; Yamane, T. J. Am. Oil Chem. Soc.
1991, 68, 6.
46. Elliot, J.M.; Parkin, K.L. J. Am. Oil Chem. Soc. 1991,
68, 171.
47. Matsumoto, W.; Nezu, T.; Ogata, H.; Kobori, S.;
Suzuki, K. Jpn. Kokai Tokkyo Koho, JP 0601,996
9401,996] (Cl.C11C3/10), 1994; Chem. Abstr. 120:
P247778h (1994).
48. Zaks, A.; Gross, A.T. PCT Int. Appl. WO 9004,033
(Cl.C12P7/64), 1990; Chem. Abstr. 113: P76643j
(1990).
49. Resck, I.S. Química Nova 1994, 17, 317.
50. Höfle, G.; Steglich, W.; Vorbrüggen, H. Angew.
Chem. Int. Ed. Engl. 1978, 17, 569.
51. Schwesinger, R. Chimia 1985, 39, 269.
52. Taber, D.F.; Amedio, J.C.; Patel, Y.K. J. Org. Chem.
1985, 50, 3618.
53. Oediger, H.; Möller, F.; Eiter, K. Synthesis 1972, 591.
54. McKay, A.F.; Kreling, M. -E. Can. J. Chem. 1957, 35,
1438.
55. Pollini, G.P.; Barco, A.; De Giuli, G. Synthesis 1972,
44.
56. Andruszkiewicz, R.; Silverman, R.B. Synthesis 1989,
953.
57. Flynn, K.G.; Nenortas, D.R. J. Org. Chem. 1963, 28,
3527.
58. Barcelo, G.; Grenouillat, D.; Senet, J.-P.; Sennyey, G.
Tetrahedron 1990, 46, 1839.
59. Khorana, H.G. Chem. Rev. 1953, 53, 145.
60. Smith, P.A.S. In The Chemistry of the Open Chain
Nitrogen Compounds; Benjamin; New York, 1965,
vol.1, cap. VI, p 277.
61. Kurzer, F.; Sanderson, P.M. J. Chem. Soc. 1962, 230.
62. Short, J.H.; Biermacher, U.; Dunnigan, D.A.; Leth,
T.D. J. Med. Chem. 1963, 6, 275.
63. Vargas, R.M. D.Sc. Thesis, Universidade Estadual de
Campinas, Campinas, Brazil, 1996.
64. Schuchardt, U.; Vargas, R.M.; Gelbard, G. J. Mol.
Catal. 1995, 99, 65.
65. Angyal, S.J.; Warburton, W.K. J. Chem. Soc. 1951,
2492.
66. Xavier, C.P.M.; Sercheli, R.; Vargas, R.M.;
Schuchardt, U. 9o Congresso Brasileiro de Catálise
(Instituto Brasileiro de Petróleo, 1997) accepted for
publication.
67. Schuchardt, U.; Lopes, O.C. BR 82 02 429, 1984;
Chem. Abstr. 101: P93246 (1984).
210 Schuchard et al.
68. Schuchardt, U.; Lopes, O.C. Anais do XI Simpósio
Ibero-Americano de Catálise (Instituto Mexicano del
Petroleo, Guanajuato, 1988) p 1505.
69. Schuchardt, U.; Lopes, O.C. Anais do I Simpósio
Nacional sobre Fontes Novas e Renováveis de Ener-
gia (MCT, Brasília, 1988) p 51.
70. Schuchardt, U.; Vargas, R.M.; Gelbard, G. J. Mol.
Catal. 1996, 109, 37.
71. Sercheli, R.; Ferreira, A.L.B.; Guerreiro, M.C.; Var-
gas, R.M.; Sheldon, R.A.; Schuchardt, U. Tetrahe-
dron Lett. 1997, 38, 1325.
72. Sercheli, R.; Ferreira, A.L.B.; Vargas, R.M.;
Schuchardt, U. In preparation.
73. Farris, R.D. J. Am. Oil Chem. Soc. 1979, 56, 770A.
74. Donnelly, M.J.; Bu’Lock, J.D. J. Am. Oil Chem. Soc.
1988, 65, 284.
75. Jandacek, R.J. Chemtech 1991, 398.
76. Jandacek, R.J. J. Chem. Ed. 1991, 68, 476.
77. Akoh, C.C.; Swanson, B.G. J. Am. Oil Chem. Soc.
1989, 66, 1581.
78. Peterson, G.R.; Scarrah, W.P. J. Am. Oil Chem. Soc.
1984, 61, 1593.
79. Mittelbach, M.; Tritthard, P. J. Am. Oil Chem. Soc.
1988, 65, 1185.
80. Staat, F.; Vermeersch, G. Rev. Fr. Corps Gras 1993,
5/6, 167.
81. Kirk-Othmer. In Encyclopedia of Chemical Technol-
ogy; John Wiley & Sons; 3rd Ed., New York, 1980,
vol. 11, p 921.
82. Zaher, F.A. Grasas y Aceites 1990, 41, 82.
83. Gateau, P.; Guibet, J.C. Rev. Inst. Fr. Pét. 1985, 40,
509.
J. Braz. Chem. Soc.
84. Rocha Filho, G.N.; Brodzki, D.; Djéga-Mariadassou,
G. Fuel 1993, 72, 543.
85. Pryde, E.H. J. Am. Oil Chem. Soc. 1984, 61, 1609.
86. Peterson, C.L.; Auld, D.L.; Korus, R.A. J. Am. Oil
Chem. Soc. 1983, 60, 1579.
87. Schwab, A.W.; Dykstra, G.J.; Selke, E.; Sorenson,
S.C.; Pryde, E.H. J. Am. Oil Chem. Soc. 1988, 65,
1781.
88. Freedman, B.; Butterfield, R.O.; Pryde, E.H. J. Am.
Oil Chem. Soc. 1985, 62, 662.
89. Freedman, B.; Kwolek, W.F.; Pryde, E.H. J. Am. Oil
Chem. Soc. 1985, 62, 663.
90. Schuchardt, U.; Lopes, O.C. Anais do 3o Congresso
Brasileiro de Energia (IBP, Rio de Janeiro, 1984) p
1620.
91. Rizzi, G.P.; Taylor, H.M. J. Am. Oil Chem. Soc. 1978,
55, 398.
92. Aguiar, L.M.G.; Silva, G.A.; Silva, C.M.A.; Ferreira,
E.B. 17a Reunião Anual da Sociedade Brasileira de
Química, (SBQ, Caxambu, 1994) abstract QO-118.
93. Weiss, T.J.; Brown, M.; Zeringue, H.J.; Feuge, R.O.
J. Am. Oil Chem. Soc. 1971, 48, 145.
94. Weiss, T.J., Brown, M., Zeringue, H.J., Feuge, R.O.
J. Am. Oil Chem. Soc. 1972, 49, 524.
95. Mattson, F.H.; Nolen, G.A. J. Nutr. 1972, 102, 1171.
96. Feuge, R.O.; Zeringue, H.J.; Weiss, T.J.; Brown, M.
J. Am. Oil Chem. Soc. 1970, 47, 56.
97. Vargas, R.M. In preparation.
98. Wallau, M.; Schuchardt, U. J. Braz. Chem. Soc. 1995,
6, 393.
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